Automated Solid-Phase DNA Synthesis and Photophysical Properties of Oligonucleotides Labeled at the 5‘-Terminus with Ru(bpy)₃²⁺

Abstract

A facile procedure for the incorporation of Ru(bpy)3 2+ in an oligonucleotide is reported. A Ru(bpy)3 2+ phosphoramidite is synthesized, and then attached to the 5‘-terminus of DNA using a standard protocol on an automated DNA solid-phase synthesizer. Photophysical studies of the Ru(II) tris-diimine complex as well as the corresponding labeled oligonucleotides demonstrate that the excited-state electron is localized on one specific bipyridine with the dipole directed toward the linkage to DNA, and that the Ru(II) excited state is long-lived when attached to the DNA.

Clathrochelate monoribbed-functionalized iron(ii) α-dioximates: synthetic pathways and structural and electrochemical features

“…3 For example, in the majority of ruthenium() tris-phenanthroline and tris-bipyridine complexes, intensively studied in recent years in this respect, only one of the three ligand fragments contains functional groups that exert an appreciable and directed influence on the physicochemical characteristics of the whole molecule. [4][5][6][7][8][9][10] In the strong field of the macrobicyclic tris-dioximate ligands, Fe 2ϩ , Co 3ϩ , Co 2ϩ and Ru 2ϩ ions have low-spin electronic configurations, short M-N distances and form clathrochelates with similar geometry and chemical properties. 11-18 However, the Fe 2ϩ ion has proved to be the most accessible and efficient template in the synthesis of macrobicyclic tris-dioximate complexes.…”

DNA structures embedded with functionalized nanomaterials for biophysical applications

“…Iondoped ruthenium bipyridine derivatives in DNA structures provide efficient luminescent labels for biosensors. They can be tagged onto the DNA backbone, sugars or base units to vary their luminescent properties and can be used to detect DNA sequence mismatches [18,[198][199][200][201].…”

Solid‐Phase Synthesis of Transition‐Metal Complexes

“…[17,58] To allow incorporation of a transition-metal complex at any position within a peptide the transition-metal building block requires both an amino functionality and a carboxylic acid group. To this end a variety of side-chain modified amino acids has been designed (29)(30)(31)(32)(33)(34)(35)(36)(37)(38)Scheme 15). [39,[59][60][61][62][63][64][65][66] Recently, a stable a-amino acid derivative incorporating a ferrocene unit at the a-position has been reported.…”

“…[39] Potential applications of these a-amino acid derivatives include peptide labelling, such as IR-sensitive labelling (piano-stool amino acids 33-36) or radiolabelling (30,32), and electron transfer studies (29, 31 or 38). [17,58,70,72] All metal-functionalised amino acids 29-38 (Scheme 15) are conceptually similar as the transition-metal complex is located in the side-chain of an a-amino acid.…”

“…These peptides serve as chiral ligands for organometallic fragments, for example, {Rh(norbonadiene)} or {PdA C H T U N G T R E N N U N G (allyl)Cl} in asymmetric catalytic reactions. [28,29] Metal-modified biomolecules prepared by SPS with one metal label attached to the terminus of the oligomer (see, for example, references [30][31][32][33][34][35]) as well as side-chain modifications of biooligomers (see, for example, references [36][37][38][39]) will not be considered further in this article. The preparation of metal-complex/peptide conjugates by solid-phase peptide synthesis has been recently summarised in microreviews and will not be covered in this article.…”